US5347828A - Organic hydride/metal hydride heat pump - Google Patents

Organic hydride/metal hydride heat pump Download PDF

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Publication number
US5347828A
US5347828A US08/083,824 US8382493A US5347828A US 5347828 A US5347828 A US 5347828A US 8382493 A US8382493 A US 8382493A US 5347828 A US5347828 A US 5347828A
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Prior art keywords
hydride
metal hydride
heat
organic
bed
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Expired - Fee Related
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US08/083,824
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English (en)
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Arthur S. Kesten
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RTX Corp
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United Technologies Corp
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Assigned to UNITED TECHNOLOGIES CORPORATION reassignment UNITED TECHNOLOGIES CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KESTEN, ARTHUR S.
Priority to US08/083,824 priority Critical patent/US5347828A/en
Priority to PCT/US1993/012106 priority patent/WO1994021973A1/en
Priority to KR1019950704047A priority patent/KR960701343A/ko
Priority to ES94904437T priority patent/ES2107807T3/es
Priority to DE69313873T priority patent/DE69313873D1/de
Priority to JP6514576A priority patent/JPH08507361A/ja
Priority to CA002158950A priority patent/CA2158950A1/en
Priority to BR9307829A priority patent/BR9307829A/pt
Priority to EP94904437A priority patent/EP0688417B1/en
Publication of US5347828A publication Critical patent/US5347828A/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/12—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type using desorption of hydrogen from a hydride
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention is directed to a heat pump, particularly a compressor-less, chlorofluorocarbon-free heat pump.
  • Heat pumps and related devices have long been used for heating, air conditioning, refrigeration, and other heat transfer applications.
  • a heat source such as a source of waste heat or a conditioned space
  • the gaseous working fluid is then compressed, condensed to a liquid, and recycled to absorb additional heat from the conditioned space.
  • the heat given up by the working fluid when it is condensed can be used for space heating, some other useful purpose, or can be rejected to the surroundings. While this cycle is widely used, drawbacks include the need for a compressor and the common use of chlorofluorocarbons as a working fluid.
  • the compressor creates noise and includes moving parts that are subject to wear and failure.
  • Chlorofluorocarbons are the subject of an international agreement that restricts their use in the future.
  • prior art systems can limit the extent to which relatively low temperature waste heat (e.g., 35° C. to 95° C.) can be used to provide space heating.
  • the present invention is directed to a compressorless, chlorofluorocarbon-free heat pump and methods for cooling and heating that use the heat pump.
  • One embodiment of the invention includes a heat pump having an organic hydride system and a metal hydride system.
  • the organic hydride system includes a vessel with a liquid space and a vapor space and a catalytic surface disposed in the vapor space.
  • the catalytic surface promotes hydrogenation of an organic dehydrogenation product to form an organic hydride and dehydrogenation of the organic hydride to form H 2 .
  • the organic hydride system also includes means for cooling the catalytic surface when it promotes hydrogenation and means for heating the catalytic surface when it promotes dehydrogenation.
  • the metal hydride system includes a metal hydride bed and means for transferring heat from a heat source to the metal hydride bed. A duct connects the vapor space of the organic hydride system with the metal hydride system.
  • Another embodiment of the invention includes another heat pump having an organic hydride system and a metal hydride system.
  • the organic hydride system includes a vessel with a liquid space and a vapor space, a catalytic surface disposed in the vapor space, a liquid-phase reaction zone in fluid communication with the liquid space, and a dehydrogenation catalyst disposed in the reaction zone.
  • the catalytic surface promotes hydrogenation of an organic dehydrogenation product to form an organic hydride and the dehydrogenation catalyst promotes dehydrogenation of the organic hydride to form H 2 .
  • the organic hydride system also includes means for cooling the catalytic surface when it promotes hydrogenation, means for providing an endothermic heat of reaction to the reaction zone, and means for transporting H 2 from the reaction zone to the vapor space.
  • the metal hydride system and duct are as described above.
  • Another embodiment of the invention includes a method of transferring heat from a heat source with a heat pump that includes a metal hydride system and an organic hydride system.
  • a heat pump that includes a metal hydride system and an organic hydride system.
  • heat is transferred from the heat source to a metal hydride bed, thereby cooling the heat source and decomposing a metal hydride in the bed to form H 2 .
  • the H 2 flows to a vapor space in the liquid hydride system and reacts with a dehydrogenation product at a catalytic surface in the vapor space to form an organic hydride and an exothermic heat of reaction.
  • the device may be operated in a regeneration mode by supplying an endothermic heat of reaction to the catalytic surface, thereby dehydrogenating the organic hydride to form H 2 .
  • the H 2 flows to the metal hydride bed and reacts with the metal hydride bed to regenerate the metal hydride and produce an exothermic heat of reaction.
  • the metal hydride may be regenerated by flowing a liquid mixture that includes the organic hydride into a reaction zone having a dehydrogenation catalyst. An endothermic heat of reaction is supplied to the reaction zone to dehydrogenate the organic hydride to form H 2 . The H 2 flows to the metal hydride bed where it regenerates the metal hydride.
  • FIG. 1 is a process flow diagram of a heat pump of the present invention configured as a cooling device.
  • FIG. 2 is a process flow diagram of another heat pump of the present invention configured as a cooling device.
  • FIG. 3 is a process flow diagram of a heat pump of the present invention configured as a space heating device.
  • the heat pump of the present invention can be used either as a cooling device, a heating device, or both. In some applications, it may be desirable to optimize the heat pump as either a cooling or heating device. In other applications, however, the heat pump may be designed as a duel use device.
  • FIG. 1 shows one embodiment of the present invention that combines a metal hydride system 2 with an organic hydride system 12.
  • the metal hydride system 2 comprises a metal hydride bed 4 that includes a metal hydride.
  • the metal hydride may be any metal hydride that endothermically dissociates to form H 2 at atmospheric pressure and a temperature above about 10° C. Preferably, the metal hydride will dissociate at a temperature above about 20° C.
  • Suitable metal hydrides include LaNi 5 H, LaNi 4 .7 Al 0 .3 H 3 , CaNi 5 H, Mg 2 NiH 4 , Fe 0 .8 Ni 0 .2 TiH 0 .6, MgH 2 , FeTiH, Fe 0 .9 Mn 0 .1 TiH, Ti 0 .98 Zr 0 .02 V 0 .45 Fe 0 .10 Cr 0 .05 Mn 1 .5 hydride and other metal hydrides known in the art.
  • Suitable materials and related storage tanks and systems can be purchased from companies such as INCO (New York, N.Y.), INCO's subsidiary MPD (Birmingham, Great Britain), Billings Corporation (Independence, Mo.), the Deutschen for Elektrometallurgie (Nuremberg, Germany), Thyssen AG (Essen, Germany), and Mannesmann AG (Dusseldorf, Germany).
  • heat from a heat source 6, such as a conditioned space is transferred to the metal hydride bed 4.
  • the metal hydride absorbs the heat and dissociates to form H 2 . Withdrawing heat from the heat source 6 cools it.
  • Any conventional means for transferring heat 8 may be used to transfer heat to the metal hydride bed 4.
  • the heat source 6 is a conditioned space
  • air from the conditioned space may be circulated through the bed 4.
  • a conventional heat transfer fluid may be used to transfer the heat.
  • Producing H 2 in the metal hydride bed 4 creates pressure and concentration differentials between the metal hydride bed and the organic hydride system 12.
  • the H 2 flows through a duct 10 to the organic hydride system 12 where it reacts with a dehydrogenation product to form a corresponding organic hydride.
  • the organic hydride may be any hydrocarbon or alcohol that can be dehydrogenated to form H 2 and at least one dehydrogenation product.
  • the organic hydride will have one to 14 carbon atoms.
  • Suitable organic hydrides include normal alkanes such as pentane, heptane, and decane, cycloalkanes such as cyclohexane, methylcyclohexane, and decalin, and alcohols such as methanol, ethanol, and propanol.
  • the organic hydride may be a blend of two or more hydrocarbon or alcohol species.
  • both the organic hydride and the dehydrogenation product will be liquids at room temperature and atmospheric pressure so they are easy to handle.
  • the organic hydride will have a single, predominant dehydrogenation product.
  • Methylcyclohexane (C 7 H 14 ) and 2-propanol ((CH 3 ) 2 CHOH) are preferred organic hydrides because they are liquids at room temperature and atmospheric pressure and dehydrogenate to H 2 and a predominant dehydrogenation product with minimal formation of side products.
  • methylcyclohexane's predominant dehydrogenation product is toluene (C 7 H 8 ) and 2-propanol's predominant dehydrogenation product is acetone ((CH 3 ) 2 CO).
  • conditions in the organic hydride system are selected to promote the reverse reactions (i.e., hydrogenation reactions) of (1) and (2) to occur.
  • the hydrogen reacts with the dehydrogenation product at a catalytic surface 32 in a vapor space 14 of a vessel 16 to form the organic hydride and an exothermic heat of reaction.
  • the vapor space 14 contains a vapor mixture of the organic hydride and its dehydrogenation product in equilibrium with a corresponding liquid mixture in a liquid space 18 of the vessel 16.
  • the liquid mixture is circulated, for example with a pump (not shown), through lines 20 and 22 to the showerheads 24 (valve 26 is closed, valve 28 is open, check valve 30 prevents flow toward the metal hydride system 2).
  • the catalytic surface 32 may comprise any catalyst that promotes the hydrogenation of the decomposition product and dehydrogenation of the organic hydride.
  • the catalytic surface 32 may comprise Ni, Cr, Co, or platinum family metals, such as Pt, Ru, Rh, Re, Ir, and Pd. Platinum family metals are preferred because they provide favorable operating conditions.
  • the catalytic surface 32 may comprise a single metal or a combination of two or more suitable metals (e.g., Pt/Re or Pt/Ir). Cluster or composite catalysts, especially those that comprise a combination of platinum family metals (e.g., Ru/Rh or Ru/Pt), are especially preferred.
  • the catalytic metal may be supported on a substrate compatible with conditions in the vapor space 14.
  • Suitable substrates include alumina, zirconia, carbon, and other materials. Depending on the requirements of a particular application, the substrate may be a coating on a metal support such as the fins or wall of a heat exchanger, a monolithic structure such as a honeycomb structure, particles disposed in a packed bed, or some other suitable form. These substrates are known in the art.
  • the catalytic surface 32 may be designed and fabricated with conventional techniques. Suitable catalytic metals and substrates may be purchased from commercial suppliers, including Englehard Corporation (Iselin, N.J.), Johnson Mathey, Inc. (Malvern, Penna.), and UOP (Des Plaines, Ill.) or may be custom fabricated for a particular application.
  • the exothermic heat of reaction generated by hydrogenating the dehydrogenation product at the catalytic surface 32 may be removed by circulating air, water, or any other suitable coolant through a heat exchanger 34.
  • the heat can be used for space heating, some other useful purpose, or merely released to the surroundings.
  • the catalytic surface 32 may have a conventional extended heat transfer surface such as fins, studs, or the like in contact with the heat exchanger 34. Any other conventional heat transfer scheme may be used to remove the exothermic heat of reaction from the vapor space 14.
  • the vapor space 14 should be maintained at a temperature that promotes the desired hydrogenation reaction.
  • the temperature required for the hydrogenation reaction which may range from about 20° C.
  • the temperature in the vapor space may be kept at less than about 150° C. If the temperature in the vapor space 14 is allowed to rise too high, the favored reaction could become the dehydrogenation reaction, which is undesirable during the cooling mode.
  • the pressure in the vapor space 14 during the cooling mode should be at or above atmospheric pressure.
  • One skilled in the art will know how to select a suitable space velocity for the reaction.
  • the heat pump may enter a regeneration mode in which the metal hydride in the metal hydride bed 4 is regenerated.
  • the catalytic surface 32 may be heated to a temperature sufficient to endothermically dissociate the organic hydride in the vapor mixture to H 2 and the dehydrogenation product.
  • the temperature required for the dehydrogenation reaction which may range from about 100° C. to about 500° C., depends on the catalyst, pressure, and organic hydride involved in the reaction.
  • the catalytic surface 32 may be heated to a temperature of at least about 300° C.
  • the endothermic heat of reaction for the dehydrogenation reaction may be supplied though the heat exchanger 34 from any heat source that is at a suitable temperature.
  • the heat may be supplied by burning a fuel such as natural gas, by electric resistance heating, or from any other suitable source.
  • the pressure in the vapor space 14 during the regeneration mode should be at or near atmospheric pressure.
  • One skilled in the art will know how to select a suitable space velocity for the reaction.
  • Producing H 2 in the organic hydride system 12 creates a pressure differential between the organic hydride system 12 and the metal hydride bed 4.
  • the metal hydride bed 4 may be cooled by circulating the liquid mixture through lines 20 and 36 (valve 26 is open, valve 28 is closed).
  • the liquid mixture returns to the organic hydride system through the check valve 30, line 22, and the showerheads 24. Spraying the liquid mixture through the showerheads 24 condenses excess dehydrogenation product and keeps sufficient organic hydride in the vapor space to form H 2 .
  • the metal hydride bed 4 may be cooled by a water loop connected to a hot water system, by using air that will oxidize the fuel burned to supply the endothermic heat of reaction, or by any other cooling system.
  • FIG. 2 shows an alternate embodiment of the present invention.
  • the metal hydride section 2 and organic hydride section 12 function as described above.
  • a valve 36 closes off access to the catalytic surface 32 and the dehydrogenation reaction takes place in a liquid phase reaction zone 38.
  • the valve 36 may be any suitable valve, such as a butterfly valve or gate valve. Alternately, any other conventional device may be used to close off access to the catalytic surface 32.
  • the liquid mixture flows to the reaction zone 38 (valves 26 and 40 are open, valve 28 is closed) where it contacts a dehydrogenation catalyst 42 suspended in the liquid in the reaction zone.
  • the catalyst 42 may be retained inside the reaction zone 38 with screens 44 or any other comparable device.
  • the dehydrogenation catalyst 42 may be any liquid phase dehydrogenation catalyst known in the art, including any of the catalysts listed above.
  • the catalyst 42 will be a carbon-supported platinum family single metal (particularly Ru and Rh) or composite catalyst (particularly Ru/Rh and Ru/Pt) similar to those described by Yasukazu Saito of the University of Tokyo and his colleagues.
  • Some of these catalysts for example a 5 wt % Ru/carbon catalyst, may be purchased from commercial suppliers such as N. E. Chemcat Co.
  • a composite catalyst may be made by adsorbing RuCl 3 and RhCl 3 or RuCl 3 and K 2 PTCl 4 in a suitable atomic ratio of Ru:Rh or Ru:Pt onto activated carbon supports from an aqueous solution at room temperature. The adsorption may take from 6 hr to about 8 hr.
  • the activated carbon should have a large specific surface area, for example about 2770 m 2 /g.
  • Such activated carbon is available from Kansai Netsukagaku Co. (Japan).
  • the adsorbed metal chlorides may be reduced to catalytic metals with an aqueous solution of NaBH 4 (900 mg/10 ml) by adding the NaBH 4 dropwise (about 1 ml/min) to the metal chloride solution. After allowing the metal chloride solution to stand for about 10 min, the carbon supported catalyst may be filtered from the solution, washed with large amounts of water, and dried. The catalyst may be dried under a vacuum at about 50° C. for about 10 hr.
  • the reaction zone 38 may be heated to a temperature sufficient to endothermically dissociate the organic hydride to H 2 and the dehydrogenation product. Dissociation proceeds at low temperatures as long as the H 2 decomposition product, in the form of gas bubbles, is permitted to leave the catalyst surface as it forms. Reaction rates are enhanced by temperatures close to the boiling point of the organic hydride. For example, if 2-propanol is dehydrogenated to acetone over a Ru/Pt/carbon catalyst, the reaction zone 38 may be heated to a temperature of about 80° C.
  • One skilled in the art will know how to select a suitable temperature and space velocity for the reaction.
  • the heat for the dehydrogenation reaction may come from any suitable source by any suitable means.
  • hot water from a hot water tank 46 may be flowed through valve 48 and a heat exchanger 50 to provide the endothermic heat of reaction.
  • the hot water may be from an industrial process or some other source.
  • the heat of reaction may be supply by any other conventional means.
  • the metal hydride bed 4 may be cooled by flowing water through line 52 (valve 54 is open). The water absorbs heat and may flow to the hot water tank 46. Alternately, the metal hydride bed 4 may be cooled by any other conventional method. If desired, the heat removed from the metal hydride bed 4 may be used for space heating or some other purpose.
  • the liquid in the reaction zone may be returned to the vessel 16 though valve 40, line 22, and showerheads 24. Additional liquid from the liquid space 18 may then be admitted to the reaction zone 38.
  • FIG. 3 shows a heat pump of the present invention that is configured as a space heating device.
  • the metal hydride bed 4 absorbs heat from a heat source 6, such as a hot water stream from an industrial process, and dissociates to form H 2 .
  • the heat source 6 may be any heat source that contains enough energy to dissociate the metal hydride bed 4.
  • the metal hydride in the bed 4 should preferably dissociate at temperatures between about 35° C. and about 95° C.
  • the H 2 flows to the vapor space 14 where it reacts with the dehydrogenation product to produce heat as described above.
  • the heat is removed through the heat exchanger 34 and is used for space heating.
  • the amount of heat removed through the heat exchanger 34 is controlled to maintain catalyst surface temperatures of less than about 150° C.
  • the metal hydride bed 4 can be regenerated as described above for the embodiment of FIG. 2.
  • Heat pumps of the present invention provide several benefits over prior art heat pumps. For example, because they have no compressor, they are quieter than prior art devices. The absence of a compressor also reduces the number of moving parts subject to wear and failure. The use of H 2 as the working fluid eliminates concerns raised by chlorofluorocarbons.
  • liquid phase dehydrogenation reaction in some embodiments of the present invention allows the use of low grade heat (for example heat at about 80° C.) as an energy source to drive the metal hydride regeneration.
  • the low grade heat also can be the heat source for operation in the primary mode when the heat pump is used for space heating.
  • the use of low grade heat can result in a high coefficient of performance.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
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US08/083,824 1993-03-23 1993-06-25 Organic hydride/metal hydride heat pump Expired - Fee Related US5347828A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US08/083,824 US5347828A (en) 1993-03-23 1993-06-25 Organic hydride/metal hydride heat pump
DE69313873T DE69313873D1 (de) 1993-03-23 1993-12-13 Organisches hydrid und metallhydrid verwendende wärmepumpe
KR1019950704047A KR960701343A (ko) 1993-03-23 1993-12-13 유기 수화물/금속 수화물 열 펌프(organic hydride/metal hydride heat pump)
ES94904437T ES2107807T3 (es) 1993-03-23 1993-12-13 Bomba de calor de hidruro organico/hidruro metalico.
PCT/US1993/012106 WO1994021973A1 (en) 1993-03-23 1993-12-13 Organic hydride/metal hydride heat pump
JP6514576A JPH08507361A (ja) 1993-03-23 1993-12-13 有機ハイドライド／金属ハイドライドヒートポンプ
CA002158950A CA2158950A1 (en) 1993-03-23 1993-12-13 Organic hydride/metal hydride heat pump
BR9307829A BR9307829A (pt) 1993-03-23 1993-12-13 Bomba de calor e processo de bomba de resfriamento de uma fonte de calor com uma bomba de calor que inclui um sistema de hidreto metálico e um sistema de hidreto orgânico
EP94904437A EP0688417B1 (en) 1993-03-23 1993-12-13 Organic hydride/metal hydride heat pump

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3581193A 1993-03-23 1993-03-23
US08/083,824 US5347828A (en) 1993-03-23 1993-06-25 Organic hydride/metal hydride heat pump

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US3581193A Continuation-In-Part 1993-03-23 1993-03-23

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US (1) US5347828A (es)
EP (1) EP0688417B1 (es)
JP (1) JPH08507361A (es)
KR (1) KR960701343A (es)
BR (1) BR9307829A (es)
CA (1) CA2158950A1 (es)
DE (1) DE69313873D1 (es)
ES (1) ES2107807T3 (es)
WO (1) WO1994021973A1 (es)

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US8727312B2 (en) 2011-04-21 2014-05-20 Hamilton Sundstrand Corporation Butterfly valve
US8993476B2 (en) 2012-10-30 2015-03-31 Jx Nippon Oil & Energy Corporation Dehydrogenation catalyst and method for producing the same
CN118448673A (zh) * 2024-04-17 2024-08-06 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) 一种密闭环境用燃料电池供氢系统
CN118495470A (zh) * 2024-05-31 2024-08-16 中国地质大学（武汉） 一种复合浆态储制氢材料及制备方法

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JP2002274803A (ja) * 2001-03-13 2002-09-25 Sekisui Chem Co Ltd 水素貯蔵・供給システム
JP4657475B2 (ja) * 2001-03-13 2011-03-23 勝 市川 水素貯蔵・供給システム
JP4662534B2 (ja) * 2004-10-01 2011-03-30 株式会社新エネルギー研究所 水素ガス生成装置
DE102005004592B4 (de) * 2005-02-01 2018-06-28 Bayerische Motoren Werke Aktiengesellschaft Speicher und/oder Druckerhöhungseinrichtung für Wasserstoff
SE530959C2 (sv) 2006-05-29 2008-11-04 Climatewell Ab Publ Kemisk värmepump med hybridsubstans
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US20120085106A1 (en) * 2010-10-07 2012-04-12 Basf Se Process for heat integration by means of a refrigeration system
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US8999880B2 (en) 2012-10-30 2015-04-07 Jx Nippon Oil & Energy Corporation Dehydrogenation catalyst and method for producing the same
CN118448673A (zh) * 2024-04-17 2024-08-06 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) 一种密闭环境用燃料电池供氢系统
CN118495470A (zh) * 2024-05-31 2024-08-16 中国地质大学（武汉） 一种复合浆态储制氢材料及制备方法

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